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Патент USA US3037966

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June 5, 1962
J. c. F. KESSLER ET AL
3,037,956
PROCESS FOR EXTRUDING A FIBER FORMING COMPOSITION
COMPRISING A LINEAR RESINOUS CONDENSATE
AND A THICKENING AGENT
Original Filed June 10, 1955
INVENTORS
P
WWW/Ma
ATTORNEYS
ice
3,037,956
Patented June 5, 1962
2
tween the flow rate determined by means of the extrusion
3,037,956
plastometer according to A.S.T.M. D.1238-52T of the
unmixed polymer and the flow rate of the polymer mixed
with the thickening agent amounts to at least 1.5.
PROQESS FOR EXTRUDING A FBER FORMING
COMPGSITI'ON COMPRISING A LINEAR RESIN
OUS CONDENSATE
AGENT
AND
A
TI-HCKENENG
This de?nition involves the content of a maximum of
2.5% by weight of water-soluble components in the poly
Jacob Christoifel Ferdinand Kessler, Velp, Arnhem, and
Ham Roelf Spreeuwers, Arnhem, Netherlands, assign
ors to N.V. Onderzoekingsinstitnut Research, Arnhem,
mer of which the ?ow rate ratio is to be determined, in
order to arrive at the most accurate indication of the
substances to be used according to the invention. As a
Netherlands, a corporation of the Netherlands
Original application June 10, 1955, Ser. No. 514,666, now
Patent No. 2,959,570, dated Nov. 8, 1960. Divided
and this application Oct. 7, 1959, Ser. No. 844,935
Claims priority, application Netherlands June 30, 1954
5 Claims. (Cl. 260—33.8)
rule, the linear polycondensation product to be processed
will contain less than 2.5% by weight of water-soluble
substances. In that case the flow rate ratio may at once
be determined with that substance. However, if the
polymer contains more than 2.5% by weight of water
This invention relates to the manufacture of self-sup 15 soluble substances, as may be the case with polycapro
porting shaped products from high molecular weight
lactam, then it is advisable to wash such polymeric sub
linear polycondensation products by means of extrusion.
stances prior to determining the ?ow rates. The sub
More particularly, the invention relates to the manu
stances (additives) for which the ?ow rate ratio is at
facture of self-supporting shaped products other than‘
least 1.5 will be preferably added to polymers also con
threads and ?lms.
taining less than 2.5% by weight of water-soluble com
This application is a division of our prior copend-ing
ponents. However, this is not necessary. In many cases
application Serial No. 514,666, ?led June 10, 1955, now
these additives may also be used in polymers having a
US. Patent No. 2,959,570.
higher content of water-soluble substances.
One of the principal objects of the present invention
In order to explain the matter of flow rate more fully
is'to provide a new and improved method for the manu 25 it should be stated that this ?ow rate determination is
facture of self-supporting shaped products from high
preferably carried out in an apparatus such as that shown
molecular weight linear polycondensation products by
in the accompanying drawing in longitudinal section.
means of extrusion wherein the dif?culties due to rapid
This apparatus comprises a metal cylinder 1 having a
changes in plasticity of these polymeric materials on
melting is avoided. A further object of the invention is
length of 16.5 cm. and a diameter of 5 cm. in which a
continuous cylindrical bore 2 having a diameter of 1
cm. is provided. In the lower port-ion of said bore a noz
zle 3 having an ori?ce of 0.21 cm. is tightly ?tted. The
bore 2 also accommodates a plunger 4 whose weight is
to provide new and improved self-supporting shaped
products that are prepared by extrusion of high molec
ular weight linear polycondensation products such as for
example linear superpolyamides. In its more speci?c
aspects, the invention has for its object the provision of
new and improved self-supporting shaped products of the
kind indicated, other than threads and ?lms.
The manner in which these and other objects and fea
tures of the invention are attained will appear more fully
from the following description thereof, in which refer
ence is made to typical and preferred procedures in order
to indicate more fully the nature of the invention, but
without intending to limit the invention thereby.
35
40
0.1 kg., said plunger being adapted to move freely up
and down within the bore. On this plunger a weight 5
of 2.06 kg. may be placed. The metal cylinder 1 ‘is
surrounded by two electric heating elements 6 and 7.
A space 8 is provided in said cylinder for receiving a
thermometer. The plunger 4 passes through a suitable
packing gland 9.
When the determination is carried out the metal cyl
inder 1 with the plunger 4 removed is ?rst heated by
means of the heating elements 6 and 7 to a temperature
The manufacture of self-supporting shaped products,
of 240° C., whereafter 7 gr. of the polymer to be tested
other than threads and ?lms, from linear polycondensa 45 are introduced into the bore 2 followed by the insertion
tion products by means of extrusion gives rise to di?icul
of the plunger. The plunger is kept without a load on
ties due to the rapid change in plasticity of those poly
the polymer for 3 minutes, but from time to time it is
.meric materials on melting, whereas said dif?culties do
pressed down to promote deaeration of the polymer.
not arise when polymeric substances such as cellulose
Thereupon the weight 5 is placed on the plunger. After
acetate and polyvinyl chloride are shaped in a corre
2 minutes this plunger should have sunk halfway down
sponding manner.
Attempts have been made to meet these di?iculties by
means of specially constructed extrusion presses. How
ever, this solution is less attractive for the processing
industry, because it necessitates procuring special equip
ment at heavy cost.
According to the present invention, it has been found
possible to prepare an extrusion material from high mo
lecular weight polyamides and similar polycondensation
the bore. If necessary, an additional pressure is exerted
on the plunger to bring it to this position. After passing
this point the polymer is given 2 minutes to flow out
freely. Thereafter the polymer stream is cut off along
55
the nozzle whereupon during the next succeeding 3 min
utes the polymer then ?owing out is separately collected,
Weighed and converted to the quantity which would have
?owed out during 10 minutes. This amount expressed in
grams is the ?ow rate.
products which may be used with satisfactory results in 60
As examples of substances which exert the desired
the usual extrusion devices, the properties of the formed
thickening action according to the present invention may
products practically not deviating from those of products
manufactured from polyamides and the like polymeric
be mentioned the following:
'
Esters of an acid of phosphorus substituted or non
substances without admixtures.
The process according to the present invention is char—
acterized in that to the polymers to be extruded there is
added such a proportion of a substance, up to a maxi
by halogen, namely alkyl phosphites, such
V65 substituted
as tributyl phosphite, diethyl phosphite, dibutyl phos
mum of 2% by weight of the polymer, which substance
tuted or non-substituted by halogen, such as diethyl ?
in the same proportion so thickens in molten condition '
chloroethyl phosphate, phenyl di-p-chlorophenyl phos
phite, and trichloroethyl phosphite, aryl phosphites, such
as triphenyl phosphite, alkyl or aryl phosphates substi
the same polymer containing up to a maximum of 2.5% 70 phate, trichloroethyl phosphate marketed under the
by weight of water-soluble components, that the ratio be
trade name Flexol 3 CF, trichloropropyl phosphate
aesaeee
cedures are set forth, it being understood, however, that
di-?-chloroethyl phosphate. Other suitable additives in
clude di-chloromethylene~m-xylene, polyallyl chloride,
tetraethyl pyrophosphate, di(chloroethyl) sulphate, tri
n-butylborate, p-xylylene dichloride, glycerol trichloro
acetate,’ diibromomethylene m-xylene, p-di(epoxy-pro
poxy) benzene, di-5~chloroethyl vinylphosphonate, 2,4-'
dimet-hylol phenol, 2,4-dimethylol 6-chlorophenol and
terephtha'lic' dialdehyde.
stances may be used.
this description is presented by way of illustration only,
and not as limiting the scope of the invention.
Example I
Granules of a polyamide having a speci?c viscosity (as
de?ned above) of 71.4, formed by the polymerization of
e-caprolactam, obtained by conducting the polymerization
Also mixtures of these sub
'
,
1%
present invention, the following examples of typical pro
marketed under the trade name Flexol CE, and ethyl’
in the presence of 0.1% by weight of orthophosphoric
acid as a stabilizer and containing about 2% by weight
'
All the foregoing substances reduce the flow rate of the
molten polymer. whereas at the aforesaid concentration of
less than 2% by weight, based on the polymer, they do
not soften‘the polymer at room' temperature. They may
therefore be regarded as high temperature thickening
of water-soluble components, were rolled during 30 sec.
with 0.2% by weight of Flexol CE as the thickening agent.
These granules were fed into a so-called table extruder
agents which have no appreciable e?ect on the polymer
atmosphere and to take off the shaped product, namely
at ordinary or room temperature.
a
a
marketed by the National Rubber Machinery. This ap
paratus makes it possible to extrude horizontally in the
,
a tube having a diameter of 25 mm. and a wall thickness
of 2 mm., in a known manner by means of a drawing
The high molecular weight polycondensation products
which are very satisfactory for use in the process accord
off device. The temperature of the extruder was main
ing tothe present invention are those which are obtained 20
tained at 260° C.
when, polymerizing e-caprolactarn and in which the ini
The extruded tube had a smooth surface and a prac
tially-jformed polymerization product is washed out to
tically cylindrical cross-section.
such a degree that the content of low molecular weight
When the same polyamide to which no thickening agent
wateresoluble components remaining therein amounts to
had been added ‘was fed to the extruder, it was not pos
25
less than 2.5 % by weight, based on the polymer.
sible to extrude a tube because the polymer merged im
In the polymerization process one generally uses phos
mediately on flowing out. Without a thickening agent it
was not possible at any temperature to obtain a shaped
phoric acid or-acetic acid as a'stabilizer and the poly
merization is carried through so far that the speci?c
product.
.viscosity of the ?nal polycaprolactam product measured
in .a‘solution of _l% by weight in 90% by weight of
30
formic acid lies between 1.1 and 1.7 and preferably be- 7
tween-1.3.and 1.7.
,
-
.
Example 11
Grains of a superpolyamide having a speci?c viscosity
of 1.6, formed by polycondensation of hexamethylene di
H."
amine and adipic acid, were continuously ted to an ex
Washingout the low molecular weight water-soluble
trusion device, a proportion of Flexol 3 CF as thickening
‘components is generally carried out until the content of
these components is-between 1.5 and 2.5% by weight, 35 agent adjusted to the supply of grains being also regularly
.fed, said proportion being 0.45% by weight relative to the
based on thepolycaprolactamv
'
.
s
- grains.
In addition, however, polyamides obtained from super
An H~shaped pro?le was formed which did not merge
polyamide-forming organic diamines and ' dicarboxylic
and which yielded an entirely satisfactory product when
acids are suitablefor processing in accordance with the
presentinvention. Thellinear polyamides to which the 40 horizontally extruded through the air onto a small con
veyor belt.
present invention relates may also be de?ned as in the
Example 111
well-known publication by R. ,L. Wakeman, “The Chemis
try of Commercial Plastics,” Reinhold Publishing Co.,
j‘1_947,,page 257, as “. . . any long-chain synthetic 'poly
Grains of a superpolyamide having a speci?c viscosity
of 1.1, formed by the polymerization of e-caprolactam,
obtained by conducting the polymerization in the presence
imeric amide which has recurring amide groups as an
integral part of the main polymer chain. . . .”
Linear
of 0.2% by weight of acetic acid as a stabilizer and con
fpolyurethanes may also be employed in ‘like manner.
taining about 2% by weight of water-soluble constituents,
‘ The objects which are shaped from the material pre
pared according to the present invention are only slightly
were mixed during 30 see. with 0.2% by weight of the
tributyl ester of phosphorous acid. These grains were
_more rigid thanrobjects consisting of the pure polymer.
processed to tubes in the same manner as in Example I
and also in this case very favorable results were obtained.
The mixing of the polymer and the thickening agent
7 maybe carried out in various ways; 7
h
,
‘It is possible to mix the substances prior to supplying
them to the extrusion device. According to a preferred
7 Example IV
amount of the thickening agent. In this way the polymer
granules are covered with a thin layer of~the thickening
agent'and an extrusion material'is obtained‘which may be
processed'in any known extrusion machine. It is also‘
’ containing about 2% by weight of water-soluble compo
Granules of a polyamide having a speci?c viscosity of
embodiment ofthe process according to the present in-v 55 1 1.4, formed by the polymerization of e-caprolactam, ob-I
ventionpolymer granules are rolled during a short time,
vtained by conducting the polymerization in the presence
for instance'during about 30 seconds, with the required
of 0.1% by weight of phosphoric acid as a stabilizer and
. ;
‘
‘
‘
nents, were rolled during 30sec. with 0.5% of dichloro
‘methylenem-xylene. _With this amount of additive the
\ ?ow rate ratio was 2.6.
possible to add the thickening agent'while the polymer is
It was found possible to extrude the thus-treated gran
ules, ‘in the manner indicated in Example I, to a tube
' being fed to the extrusion‘ device so that'the mixture of
the two 'is obtained en route through the extrusion device.
having a smooth surface a'nda practically cylindrical
,Pro?les, thin rods, technical articles, toy articles, hollow 65 cross-section.
objects, such‘ as tubes and bottles, and other massive
' shapes may be easily shaped in the known extrusion ma?
, , chines-with extrusion material-prepared'faccording toithe ,
*fprocessofthepresentinvention.
'
'
'
amine and adipic acid; and: which’ were rolled in the
As indicated ‘above, in, "addition, to, .polycondensation
‘ products made'ffrom a single monomeric substance'such. .
as e-caprolactam, rrcopolyjcondensation. products or mix
'
'
In order to indicate still more fully the nature .ot?ithei
manner mentioned inlExample I with 0.5% by weight
of triphenyl phosphite, were continuously supplied to an
extrusion device of the above-mentioned type and were
'formed' to a tube by means of said extrusion device.
'75 - A'ttube was obtained which had a smooth surface and
’ tures '“ot'these various products" may vbe employed 'for A '
1 processing according to the present invention. I '
Example V
Granules of a polyamiderhaving a speci?c viscosity of
1.6, formed by polycondensation of .hexamethylene di
-
aos'zgeee
5
6
a practically circular cross-section. In this case the ?ow
What is claimed is:
1. A process for the preparation of massive self-sup
porting shaped extrusion products of substantial cross
section from extrusion materials consisting essentially of
rate ratio was 12.5.
Example VI
Granules of a polyamide having a speci?c viscosity of
high molecular weight ?ber-forming linear polycondensa
1.1, formed by the polymerization of e-caprolactam, ob
tained by conducting the polymerization in the presence
tion products selected from the class consisting of long
chain synthetic linear polyamides which have recurring
or" 0.2% by weight of acetic acid as a stabilizer and con
amide groups as ‘an integral par-t of the main polymer
taining about 2% by weight of water-soluble components,
were rolled during 30 sec. with 0.5% by weight of p
di(epoxy-propoxy) benzene. These granules were proc
10
chain and linear polyurethanes, said process consisting of
preparing a physical mixture of (a) said polycondensa
tion product and (b) from 0.2% up to a maximum of
essed to tubes in the same manner as in Example I and
also in this case very satisfactory results were obtained.
2%, by weight of said polycondensation product, of a
high temperature thickening agent selected from the class
Example VII
consisting of di-chloromethylene-m-xylene, p-xylylene di
Polyurethane granules of commercial quality were 15 chloride, and di-bromomethylene-m-xylene, and said high
temperature thickening agent when present in the .same
rolled with tributyl phosphite until they had taken on
proportion having no appreciable effect on said polycon
0.5% by weight of this substance. With this quantity the
densation product at ordinary room temperature but so
flow rate ratio was 1.8 (determined at 210° C. in con
thickening, in molten condition, the same polycondensa
nection with the low melting point of polyurethane).
The polyurethane used in this example was a linear poly 20 tion product containing up to a maximum of 2.5% by
weight of Water-soluble components, that the ratio be
mer having a molecular weight of about 15,000 to 18,000
tween the ?o-w rate, determined by means of the extrusion
and was made by the condensation of hexamethylene di
plastometer according to A.S.T.M. D.1238-52T, of the
isocyanate and 1,4-butanediol in the well-known manner
unmixed polycondensation product and the flow rate of
(e.g., see Rinke et al. US. Patent No. 2,511,544 and Catlin
the polycondensation product mixed with the high tem
US. Patent No. 2,284,637) it being understood that
perature thickening agent amounts to at least 1.5, and
neither the particular polyurethane per se nor its manner
then rapidly melt extruding the resulting physical mixture
of preparation constitutes a part of the present invention.
of high molecular Weight linear polycondensation prod
The granules of polymer thus rolled were extruded to
uct and high temperature thickening agent under condi
tubes in ‘the manner indicated in Example I, said tubes
having a practically circular cross-section.
30 tions of elevated temperatures at which said mixture is
molten into a massive self-supporting shaped product of
Example VIII
substantial cross-section, thereby ‘at least greatly minimiz
ing dif?culties vdue to rapid changes in plasticity of said
Polyamide granules having a speci?c viscosity of 1.2,
high molecular weight linear polycondensation products
prepared by the polymerization of e-caprolactam in the
presence of 0.1% by weight of phosphoric acid and con
35 per se on melting.
2. A process according to claim 1 wherein the high
temperature thickening agent is admixed with the poly
condensation product by rolling the latter, in granular
taining 10% by weight of water-soluble substances, were
rolled with p-xylylene dichloride until they had taken on
1.0% by weight of this substance.
The granules of polymer thus rolled may be processed
form, with the thickening agent until the granules are
to tubes in the manner indicated in Example I, said tubes 40 covered with a thin layer of the thickening agent.
3. A process according to claim 1 wherein di-chloro
having an almost circular cross-section.
methylene-m-xylene is added to a linear polyamide as
We ‘are aware of French Patent No. 912,504, and do
said high temperature thickening agent.
’
not wish to be understood as claiming anything disclosed
or suggested therein.
4. A process according to claim 1 wherein p-xylylene
'le speci?c examples of preferred methods and in 45 dichloride is added to a linear polyamide as said high tem
perature thickening agent.
gredients embodying the present invention have been de
5. A process according to claim 1 wnerein di-bromo
scribed above, it will be apparent that many changes and
methylene-rn-xylene is added to a linear polyamide as said
modi?cations may be made in the methods of procedure
high temperature thickening agent.
and ingredients recited without departing from the true
spirit of the invention. It will therefore be understood 50
References Cited in the ?le of this patent
that the examples cited and the particular proportions,
UNITED STATES PATENTS
ingredients and methods set forth above are intended to
be illustrative only, and are not intended to limit the scope
of the invention.
55
2,631,993
2,769,798
2,805,170
Morgan _____________ __ Mar. 17, 1953
Meis et 'al _____________ __ Nov. 6, 1956
Bell _________________ __ Sept. 3, 1957
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